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WO2011088743A1 - Matériau sous forme d'écaille ayant des propriétés différentes sur ses côtés avant et arrière et son procédé de préparation - Google Patents

Matériau sous forme d'écaille ayant des propriétés différentes sur ses côtés avant et arrière et son procédé de préparation Download PDF

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Publication number
WO2011088743A1
WO2011088743A1 PCT/CN2011/000081 CN2011000081W WO2011088743A1 WO 2011088743 A1 WO2011088743 A1 WO 2011088743A1 CN 2011000081 W CN2011000081 W CN 2011000081W WO 2011088743 A1 WO2011088743 A1 WO 2011088743A1
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Prior art keywords
polar solvent
sodium
dissolved
continuous phase
dispersed phase
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English (en)
Chinese (zh)
Inventor
杨振忠
梁福鑫
刘继广
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • Sheet material having different properties on front and back surfaces and preparation method thereof
  • the invention belongs to the technical field of materials, and relates to a sheet material having different properties on the front and back surfaces and a preparation method thereof.
  • a Pickering emulsion such an emulsion is referred to as a Pickering emulsion.
  • a Pickering emulsion Unlike the emulsifying mechanism of traditional surfactants and polymer emulsifiers, although solid particles do not reduce the interfacial tension [E. Vignati, R. Piazza, TP Lockhart. Langmuir 2003, 19, 6650-6656.], the solid particles have High emulsifying ability and excellent stability of the Pickering emulsion, which is related to the type and size of the particles [BP Binks, S. 0. Lumsdon. Langmuir 2001, 17, 4540-4547].
  • the Pickering property of the solid particles can be combined with the ability to reduce the surface tension, which greatly enhances the emulsifying ability and emulsion stability.
  • people began to study micro- or nano-particles (Janus) with dual properties (hydrophilic/hydrophobic) on the surface. The results show that Janus particles can better reduce surface tension at the oil-water interface compared to Pickering particles [BP Binks, PDI Fletcher. Langmuir 2001, 17, 4708-4710], playing a better emulsification [N. Glaser, DJ Adams, A. Boker, G. Krausch. Langmuir 2006, 22, 5227-5229.].
  • the Janus structure sheet material is blended with two polymers which are compatible with the materials on both sides of the sheet in a certain processing mode, and the inorganic material is obtained.
  • Imitation shell structure or imitation fish scale structure alternately organic layered [ZY Tang, NA Kotov, S. Magonov, B. Ozturk. Nature mater, 2003, 2, 413-418; P. Podsiadlo, AK Kaushik and NA Kotov Science, 2007, 318, 80-83; LJ Bonderer, AR Studart, LJ Gauckler. Science, 2008, 319, 1069-1073; E. Munch, ME Launey and RO Ritchie.
  • this layered hybrid structural material not only improves the mechanical properties of the material, but also alternates the hybridization of the two organic layers into a material.
  • Functionalization provides a wider range of spaces, such as the choice of hydrophobic and oleophobic organic materials to provide a layered material with high barrier properties.
  • Such materials which can improve the mechanical properties of materials (such as strengthening and toughening) and material functionalization (such as barrier properties), will play an important role in the controllable preparation of high-strength, high-toughness biomimetic materials and noise-reducing damping materials.
  • the Janus structure sheet material is widely composed and may be composed of an inorganic material or an organic material, or even composed of an inorganic material and an organic material, and the Janus structure sheet material may have a pore structure or may have no pores. structure.
  • the Janus structure sheet material is not only tunable in composition and properties, but also has a controllable microstructure and size.
  • the Janus structure sheet material having different compositions, structures and properties can be designed according to practical application requirements.
  • the Janus structure sheet material has a thickness greater than 5 nm and less than 50 ⁇ m ; and the Janus structure sheet material has a size greater than 50 nm and less than 500 ⁇ m.
  • the composition ratio of the sides of the Janus structure sheet material is adjustable from 1:100 to 100:1.
  • the different surfaces of the Janus structure sheet material have different responses to electricity, magnetism, light, etc., and thus can be used in the material field;
  • the Janus structure sheet material has an emulsification property in an organic, inorganic dispersed phase or a different organic dispersed phase.
  • the inorganic sheet composite has a different orientation at the interface.
  • the present invention provides a Janus structure sheet material having different properties on the front and back surfaces, including a substrate and a different material composition on the front and back surfaces of the substrate; wherein the material on the front surface of the substrate is at least one a layer; the material on the reverse surface of the substrate is at least one layer;
  • the material on the front and back surfaces of the substrate is selected from any one of two types of materials: a material obtained by compounding an inorganic material with an organic chemical group, and an organic material.
  • the inorganic material is selected from the group consisting of Si0 2 ,
  • n an integer of 0 ⁇ 121
  • the organic material is selected from the group consisting of urea-formaldehyde resins, Melamine resin, polyacrylonitrile, epoxy resin, phenolic resin, polyamide, polyurea, polysulfonamide, polyurethane, polyester, polyoxypropylene, polydimethylsilane, polyisobutylene polystyrene, polybutadiene , polyisoprene, gum arabic, sodium alginate, agar, sodium polyphosphate, sodium polysilicate, Carboxymethylcellulose, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolysate of ethylene-maleic anhydride copolymer, sodium salt hydrolyzate of ethylene methyl ether-maleic anhydride copolymer
  • the copolymer of acrylic acid or methacrylic acid and styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile refers specifically to Any of the following copolymers: a copolymer of acrylic acid as a comonomer copolymerized with any of the following comonomers: styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, Copolymers of isobutylene, acrylate, methacrylate and acrylonitrile; or methacrylic acid as a comonomer copolymerized with any of the following comonomers: styrene, ethylene, vinyl alcohol, vinyl acetate , methacrylamide, isobutylene, acrylate, methacrylate and acrylonitrile.
  • the polymer formed by the polycondensation reaction of the polyvinylbenzenesulfonic acid with polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin or casein specifically refers to any one of the following copolymers: polyvinylbenzene
  • the above-mentioned front and back surfaces have different properties of the Janus structure sheet material, the thickness is 5 ⁇ - 50 ⁇ , and the length and width are both 50 ⁇ - 500 ⁇ ; the material on the front surface of the substrate and the bottom surface of the substrate are The weight ratio of the material on the substrate is 1:100-100:1; the Janus structure sheet material having different properties on the front and back surfaces has a porous structure; the porous structure has a pore diameter of 1 to 50 nm.
  • the method for preparing the above-mentioned front and back surfaces having different properties of the sheet material is obtained by materializing the emulsion oil-water interface, that is, by chemical reaction or physical adsorption at the interface between the discontinuous phase droplets and the continuous phase of the emulsion.
  • the method forms a layer of inorganic material, organic material and inorganic and organic composite material, and the spherical shell layer may be continuous or discontinuous.
  • continuous shells they can be ground into pieces.
  • the size of the fragments can be achieved by controlling the grinding process.
  • the thickness of the fragments can be achieved by controlling the concentration of the reactants.
  • the shell can be used directly as a shell.
  • the above-mentioned sheet material is used, and it can be further used for grinding.
  • the thickness and size of the sheet are related to conditions such as the concentration of the reactant.
  • the preparation process of the Janus structure sheet material having the dual properties described above may be prepared in a one-step process or a multi-step process.
  • the multi-step preparation method refers to further reacting or depositing other substances on the inner surface, or the outer surface, or the inner and outer surfaces of the shell layer after forming the primary shell layer, thereby obtaining a sheet-like material having different inner and outer surface properties.
  • the following describes in detail various methods 1 to 6 of the present invention for preparing Janus structure sheet materials having different properties on the front and back surfaces:
  • the method 1 is as follows: 1) or step ⁇ ):
  • Step 1) dispersing a dispersed phase composed of a dispersed phase reactant, a coupling agent and a non-polar solvent under an action of an emulsifier in a continuous phase composed of a continuous phase reactant and a polar solvent to form an emulsion.
  • a dispersed phase composed of a dispersed phase reactant, a coupling agent and a non-polar solvent under an action of an emulsifier in a continuous phase composed of a continuous phase reactant and a polar solvent to form an emulsion.
  • an acid or a base is added, and the reactant dissolved in the continuous phase and the dispersed phase is dispersed in the dispersion.
  • the phase reacts with the interface of the continuous phase to directly form a Janus structure sheet material having different properties on the front and back surfaces; wherein the viscosity of the non-polar solvent in the dispersed phase is lower than that in the continuous phase a viscosity of the polar solvent, a volume ratio of the dispersed phase to the continuous phase is less than 5 and more than 0.5, and a reaction temperature is not lower than a melting point of the non-polar solvent and the polar solvent, and is not higher than a boiling point of the non-polar solvent and the polar solvent;
  • An acid or a base is added under the condition of a pH of 2-10, and the reactant dissolved in the continuous phase and the dispersed phase reacts at the interface of the dispersed phase and the continuous phase, on the surface of the dispersed phase droplet Forming a core-shell structure product having a continuous shell layer of a Janus structure, removing the core in the core-shell structure product having the continuous shell layer of the Janus structure, and pulverizing to obtain a Janus structure sheet material having different properties on the front and back surfaces;
  • the viscosity of the non-polar solvent in the dispersed phase is higher than the viscosity of the polar solvent in the continuous phase, and the volume ratio of the dispersed phase to the continuous phase is greater than 0 and less than 5, and the temperature of the reaction is not Lower than the melting point of the non-polar solvent and the polar solvent, and not higher than the boiling points of the non-polar solvent and the polar solvent;
  • the method 2 includes the following steps:
  • the ABC triblock copolymer is placed in an emulsion, and the A chain segment and the C segment of the ABC triblock copolymer are respectively distributed toward the aqueous phase and the oil phase under the induction of the dispersed phase and the continuous phase solvent, in the ultraviolet Under the condition of light irradiation or temperature of 50-100 ° C, the B segment in the ABC triblock copolymer undergoes in-situ polymerization at the interface of the emulsion, and the B segment is obtained as the intermediate layer of the shell, A a hollow microsphere having a Janus structural shell layer on both sides of the middle layer of the shell layer respectively, and pulverizing to obtain a Janus structure sheet material having different properties on the front and back surfaces;
  • the method 3 includes the following steps 1) to 2):
  • step 1) is any one of the following steps a) to b):
  • Step 2) if the decomposition temperature of the initiator is lower than the temperature of the polycondensation reaction, the radical polymerization reaction monomer is first subjected to radical polymerization to obtain a primary shell layer, and then the unpolymerized polycondensation sheet is initiated.
  • the body or prepolymer undergoes a polycondensation reaction outside the primary shell layer to form hollow microspheres having a Janus structure shell layer, and after pulverization, a Janus structure sheet material having different properties on the front and back surfaces is obtained; if the initiator is decomposed
  • the monomer or prepolymer which initiates the polycondensation reaction is subjected to a polycondensation reaction to obtain a primary shell layer; and the unrepolymerized radical reactive monomer is further induced in the primary shell layer.
  • a radical polymerization reaction occurs on the inner side to form hollow microspheres having a Janus structural shell layer, and after pulverization, a Janus structure sheet material having different properties on the front and back surfaces is obtained.
  • the method 4 includes the following steps 1) to 2): Wherein the step 1) is any one of the following steps a) to (f): Step a): dissolving the inorganic reactant in a non-polar solvent as a dispersed phase under the action of an emulsifier Forming an emulsion in a continuous phase composed of a polar solvent in which a monomer or prepolymer of a polycondensation reaction is dissolved;
  • the phase is dispersed in a continuous phase composed of a polar solvent to form an emulsion;
  • Step 0 Dispersing a polar solvent as a dispersed phase under the action of an emulsifier, radical polymerization of a radically polymerizable monomer dissolved in an inorganic reactant, dissolved in a nonpolar solvent, and dissolved in a nonpolar solvent Forming an emulsion in a continuous phase composed of a non-polar solvent of an initiator;
  • Step 2) first, the inorganic reactant is subjected to a sol-gel reaction at the interface between the dispersed phase and the continuous phase to obtain a primary shell layer, and then the monomer or prepolymer of the polycondensation reaction which is not polymerized is in the primary shell.
  • a polycondensation reaction occurs on the outer side of the layer to form hollow microspheres having a Janus structural shell layer, and after pulverization, a Janus structure sheet material having different properties on the front and back surfaces is obtained.
  • the method 5 includes the following steps 1) to 3):
  • step 1) is any one of the following steps a) to d):
  • the polymer is phase-separated and deposited at the interface between the dispersed phase and the continuous phase to form a crosslinked
  • the step 2) is the following steps a') or b') :
  • Step a' adding a prepolymer of a monomer or a resin dissolved in the continuous phase solvent to the reaction system of the step 1) to carry out a polycondensation reaction, forming a new shell on the outer side of the primary shell layer a layer forming hollow microspheres having a Janus structural shell;
  • Step b') further adding a polymer having an opposite charge to the polymer obtained in the step 1) to the reaction system of the step 1), so that the polymer obtained in the step 1) is opposite to the one described
  • the charged polymer undergoes electrostatic attraction, forming a new shell layer outside the primary shell layer to form hollow microspheres having a Janus shell layer;
  • Step 3) pulverizing the hollow microspheres having the Janus structural shell layer obtained in the step 2) to obtain the Janus structure sheet material having different properties on the front and back surfaces;
  • the method 6 includes the following steps 1) to 2):
  • step 1) is any one of the following steps a) to b):
  • Step 2) The step 1) raising the temperature of the reaction system causes the radical polymerizable monomer dissolved in the polar solvent to be polymerized at the emulsion interface to obtain hollow spheres having different compositions and properties on both sides, crushing or The Janus structure sheet material having different properties on the front and back surfaces is obtained without pulverization.
  • the structure of the dispersed phase reactant is X n MR m , preferably ethyl orthosilicate; wherein M is Si, Ti, Sn, A1 or Zr; X is Na, Mg or K , n is 0, 1 or 2; R is Cl, OS0 4 , OCH 3 , OCH 2 CH 3 , OCH(CH 3 ) 2 , OCH 2 CH 2 CH 2 CH 3 or S0 4 , m is 1, 2, 3 Or 4; the non-polar solvent is selected from at least one of an aromatic hydrocarbon, a paraffin, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, an aliphatic hydrocarbon, and ethyl acetate, preferably toluene; the coupling Agent
  • the A block is a hydrophilic polymer segment selected from the group consisting of polyoxyethylene, polymaleic anhydride, polymethyl methacrylate and polyacrylic acid.
  • B block is a reactive olefin or alkyne polymer segment selected from polyacetylene, polybutadiene or polyisoprene
  • C block is a hydrophobic polymer segment, selected At least one of polyoxypropylene, polyoxybutylene, polystyrene, polyolefin, and polysiloxane
  • the solvent as the dispersed phase and the continuous phase are respectively selected from mutually incompatible polarities a solvent and a non-polar solvent; wherein the non-polar solvent is at least one selected from the group consisting of aromatic hydrocarbons, paraffin wax, n-hexane, carbon tetrachloride, chloroform, cyclohexane, dichloromethan
  • the monomer or prepolymer of the polycondensation reaction is selected from the group consisting of acrylonitrile, vinyl acetate, urea resin (urea-formaldehyde prepolymer), melamine resin (melamine-formaldehyde prepolymer), phenolic Resin (phenol-formaldehyde prepolymer), melamine modified urea-formaldehyde resin, polyethylene glycol modified urea-formaldehyde resin, polypropylene glycol modified urea-formaldehyde resin, polyethylene glycol modified melamine resin with molecular weight of 200-2000, molecular weight 200-2000 polypropylene glycol modified melamine resin, polyvinyl alcohol modified urea formaldehyde resin, resorcin modified urea resin, hydroquinone modified urea formaldehyde resin, phenol modified urea resin, phenol and melamine copolymerization Modified urea-
  • the inorganic reactant has a structural formula of X n MR m: wherein M is Si, Ti,
  • Sn, A1 or Zr X is Na, Mg or K, n is 0, 1 or 2; R is Cl, OS0 4 , OCH 3 , OCH 2 CH 3 , OCH(CH 3 ) 2 , OCH 2 CH 2 CH 2 CH 3 or S0 4 , m is 1, 2, 3 or 4; or
  • the emulsifier is used in an amount of 1% by weight of the initial
  • the temperature is 60 -90 ° C, preferably 70 ° C
  • the reaction time is 0.5-72 hours, preferably 2-16 hours
  • the molar ratio of the monomer of the radical polymerization reaction to the initiator is 10: 1-1000 : 1; preferably 50: 1: 500: 1
  • the temperature of the radical polymerization is 20-90 ° C
  • the reaction time is 0.5-72 hours, preferably 2-16 hours.
  • the prepolymer of the monomer or the resin dissolved in the continuous phase solvent in the step 1) a) is selected from the group consisting of acrylonitrile, vinyl acetate, urea formaldehyde resin (urea-formaldehyde prepolymer), Melamine resin (melamine-formaldehyde prepolymer), phenolic resin (phenol-formaldehyde prepolymer), melamine modified urea-formaldehyde resin, polyethylene glycol modified urea-formaldehyde resin, polypropylene glycol modified urea-formaldehyde resin, molecular weight 200 ⁇ 2000 Polyethylene glycol modified melamine resin, polypropylene glycol modified melamine resin with molecular weight of 200 ⁇ 2000, polyvinyl alcohol modified urea formaldehyde resin, resorcin modified urea resin, hydroquinone modification Urea-formaldehyde resin, phenol-modified urea-formalde
  • the continuous phase reactant and the dispersed phase reactant in step 1) b) are each selected from the group consisting of diamines, polyamines, glycols, polyols, dihydric phenols, polyhydric phenols, dibasic acid chlorides, polyacid chlorides, and binary At least one of a sulfonyl chloride, a polysulfonyl chloride, a diisocyanate, a polyisocyanate, a bischloroformate, an epoxy resin prepolymer, and an organosiloxane prepolymer;
  • the dispersed phase free radical polymerizable monomer in the step 1) c) is selected from the group consisting of styrene, butadiene, isoprene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid.
  • Tert-butyl ester isobutyl methacrylate, ethyl cinnamic acid acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, propylene oxide, dimethyl silane, vinyl butyl ester At least one of isobutylene or vinyl acetate, divinylbenzene, ethylene glycol dimethacrylate and diallyl terephthalate;
  • the dispersed phase polymer and the continuous phase polymer forming the primary shell layer in step 1) d) are each selected from the group consisting of polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin, casein, gum arabic, sodium alginate, agar, Sodium polyphosphate, sodium polysilicate, carboxymethyl cellulose, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolyzate of ethylene-maleic anhydride copolymer, vinyl methyl ether-butylene Sodium salt hydrolysate of dianhydride copolymer, sodium salt hydrolyzate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate , methacrylate or acrylonitrile copolymerization At least one of a copolymer
  • the monomer or resin prepolymer dissolved in the continuous phase solvent in step 2) a') is selected from the group consisting of acrylonitrile, vinyl acetate, urea formaldehyde resin (urea-formaldehyde prepolymer), melamine resin (melamine).
  • Formaldehyde prepolymer phenolic resin (phenol-formaldehyde prepolymer), melamine modified urea-formaldehyde resin, polyethylene glycol modified urea-formaldehyde resin, polypropylene glycol modified urea-formaldehyde resin, polyethylene glycol modified molecular weight of 200 ⁇ 2000 melamine resin, polypropylene glycol modified melamine resin with molecular weight of 200 ⁇ 2000, polyvinyl alcohol modified urea-formaldehyde resin, resorcinol modified urea-formaldehyde resin, hydroquinone modified urea-formaldehyde resin, phenol modification Urea-formaldehyde resin, phenol and melamine copolymerization modified urea-formaldehyde resin, polyvinyl alcohol and melamine copolymerization modified urea-formaldehyde resin, resorcinol and melamine copolymerization modified
  • the polymer having opposite charge to the polymer obtained in the step 2) b) is selected from the group consisting of polyvinylpyridinium bromide, polyvinylpyrrolidone, gelatin, casein, gum arabic, sodium alginate, agar , sodium polyphosphate, sodium polysilicate, carboxymethyl cellulose, sodium salt hydrolysate of styrene-maleic anhydride copolymer, sodium salt hydrolyzate of ethylene-maleic anhydride copolymer, vinyl methyl ether-cis-butane Sodium salt hydrolysate of enedic anhydride copolymer, sodium salt hydrolysate of isobutylene-maleic anhydride copolymer, acrylic acid or methacrylic acid with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylic acid a copolymer obtained by copolymerization of an ester, a methacrylate or an acrylonitrile
  • the temperature is 60-90 ° C, preferably 70 ° C
  • the time is 0.5-72 hours, preferably 2-16 hours
  • the pH is 2-10
  • the stirring speed is 50- 16000r/min, preferably 150-12000r/min
  • the molar ratio of the reactive phase reactant to the continuous phase reactant reactive functional group is 1:1;
  • Is 60-90 ° C, preferably 70 ° C, time is 0.5-72 hours, preferably 2-16 hours, stirring speed is 50-16000r / min, preferably 150-12000r / min;
  • the molar fraction ratio of the dispersed phase radical polymerizable monomer to the initiator is 10: 1-1000: 1; preferably 50: 1-500: 1 , the temperature is 20-90 ° C, the time is 0.5-72 hours, preferably 2-16 hours;
  • Step 1) The pH of the reaction system described in d) is 2-10;
  • the temperature is 60-90 ° C, preferably 70 ° C
  • the time is 0.5-72 hours, preferably 2-16 hours
  • the pH is 2-10
  • the stirring speed is 50.
  • - 16000r / min preferably 150-12000r / min
  • the pH of the reaction system described in step 2) b') is 2-10;
  • the emulsifier is selected from the group consisting of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer, a sodium salt hydrolyzate of an ethylene-maleic anhydride copolymer, and a sodium salt hydrolyzate of a vinyl methyl ether-maleic anhydride copolymer.
  • the dispersed phase solvent is at least one selected from the group consisting of aromatic hydrocarbons, paraffin, carbon tetrachloride, chloroform, cyclohexane, dichloromethane, aliphatic hydrocarbons and ethyl acetate;
  • the continuous phase solvent is at least one selected from the group consisting of water, ethylene glycol, propylene glycol, glycerin, tetrahydrofuran, and N, N-dimethylformamide.
  • the radical polymerizable monomer dissolved in the non-polar solvent is selected from the group consisting of styrene, butadiene, isoprene, methyl methacrylate, ethyl methacrylate, and methacrylic acid Ester, tert-butyl methacrylate, isobutyl methacrylate, methacrylic acid, ethyl cinnamate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, propylene oxide, dimethyl At least one of silane, vinyl butyl ester, isobutylene or vinyl acetate, divinyl benzene, ethylene glycol dimethacrylate and diallyl terephthalate; said dissolving in a non-polar solvent
  • the radical polymerization initiator is selected from the group consisting of azobisisobutyronitrile, azobisisoheptanenitrile, dibenzo
  • the radically polymerizable monomer dissolved in a polar solvent is selected from the group consisting of acrylamide, hydrazine, hydrazine- At least one of dimethyl bis acrylamide, acrylic acid, methacrylic acid, vinyl alcohol, hydrazine-hydroxymethyl acrylamide;
  • the radical polymerization initiator dissolved in a polar solvent is selected from the group consisting of potassium persulfate and sulfuric acid Iron, ammonium persulfate, a mixture of persulfate and thiosulfate, a mixture of persulfate and sulfite, a mixture of persulfate and fatty amine or a persulfate and fatty diamine
  • At least one of the components of the composition preferably at least one of potassium persul
  • the complex coacervation reaction utilizes electrostatic attraction between two or more water-soluble polymer molecules having opposite charges, and the formed agglomerates are phase-separated in the aqueous phase and A method of depositing at the interface and forming a polymer after cross-linking and solidification.
  • the thickness of the Janus structure sheet material can be controlled by changing the amount of the reactant.
  • the pulverization method is various commonly used pulverization methods.
  • Can The size of the Janus structure sheet material can be adjusted from 50 nm to 500 ⁇ m by controlling the ball mill or colloid mill grinding time and the grinding method, preferably 50 ⁇ to 100 ⁇ .
  • the emulsion includes a type emulsion of a normal phase emulsion, an inverse emulsion, a microemulsion, a reverse phase microemulsion, and the like.
  • the low temperature grinding temperature ranges from 0 °C to 170 °C.
  • Figure 1 is a silica prepared on Example 1 of the present invention having an amine group on one side and a phenyl group on the other side.
  • Figure 2 is a scanning electron micrograph of a Janus sheet material of a silicon dioxide having an epoxy group on one side and a phenyl group on the other side prepared in Example 2 of the present invention.
  • Example 3 is a photograph showing the emulsification performance of a sheet material of Janus structure having different properties on both sides prepared in Example 3 of the present invention.
  • the left side is a system without a Janus sheet
  • the right side is a system emulsified after adding a Janus sheet. .
  • Example 4 is a scanning electron micrograph of a sheet material of Janus structure having different properties on both sides prepared in Example 3 of the present invention, and the embedded figure is the sulfonated polystyrene pellet adsorbed on the Janus aramid side of Example 3. Scanning electron micrograph of a 30 nm) Janus structure sheet material.
  • Fig. 5 is a scanning electron micrograph of a porous Janus structure sheet material prepared in Example 4 of the present invention, and the inlaid photograph is a transmission photograph of the porous Janus structure sheet material of Example 4 of the present invention.
  • Fig. 6 is a transmission electron micrograph of a porous Janus structure sheet material prepared in Example 5 of the present invention.
  • Fig. 7 is a scanning electron micrograph of an organic Janus structure sheet material having an amine group on one side and a pentadecyl group on the other side prepared in Example 6 of the present invention.
  • Figure 8 is a scanning electron micrograph of a urea-formaldehyde resin/polystyrene Janus sheet material prepared in Example 8 of the present invention.
  • Figure 9 is a scanning electron micrograph of a silica/melamine resin Janus sheet material prepared in Example 11 of the present invention.
  • Figure 10 is a scanning electron micrograph of a polystyrene/silica Janus sheet material prepared in Example 14 of the present invention.
  • Figure 11 is a scanning electron micrograph of a polydivinylbenzene/silica Janus sheet material Janus sheet material prepared in Example 15 of the present invention.
  • Figure 12 is a scanning electron micrograph of a uric acid/melamine resin Janus sheet material prepared in Example 16 of the present invention.
  • Figure 13 is a scanning electron micrograph of a polyethylene glycol modified urea-formaldehyde resin/gelatin Janus sheet material prepared in Example 17 of the present invention.
  • Figure 14 is a scanning electron micrograph of a polyurethane/urea resin Janus sheet material prepared in Example 18 of the present invention.
  • Figure 15 is a scanning electron micrograph of an epoxy resin/polyvinylpyrrolidone Janus sheet material prepared in Example 19 of the present invention.
  • Figure 16 is a scanning electron micrograph of a polystyrene/urea resin Janus sheet material prepared in Example 20 of the present invention.
  • Figure 17 is a scanning of the polydivinylbenzene/gelatin Janus sheet material prepared in Example 21 of the present invention. Electron micrograph.
  • Figure 18 is a scanning electron micrograph of gelatin / sodium alginate Janus sheet material prepared in Example 22 of the present invention.
  • Figure 19 is a scanning electron micrograph of a polyacrylamide/polystyrene Janus sheet material prepared in Example 23 of the present invention.
  • Figure 20 is a scanning electron micrograph of a polymethyl methacrylate/polystyrene layered material modified with a silica sheet material prepared in Example 1 of the present invention.
  • Figure 21 is a polarizing microscope photograph of the emulsion prepared from the Janus sheet material provided in Example 1.
  • Figure 22 is a photograph of a silica Janus sheet having an amine group on one side and a phenyl group on the other side in the oil-water separation process in Example 1 of the present invention.
  • the invention is further illustrated by the following specific examples, but the invention is not limited to the following examples.
  • concentrations described in the following examples are all mass percent concentrations unless otherwise specified.
  • the compounds described in the following examples are commercially available from commercially available sources unless otherwise stated.
  • the ethylene-maleic anhydride copolymer has a weight average molecular weight of 200 to 20,000 in the sodium salt hydrolyzate of the ethylene-maleic anhydride copolymer, and is commercially available from Aldrich as CAS: 31959-78-1, vinyl methyl
  • the ethylene methyl ether-maleic anhydride copolymer has a weight average molecular weight of 600 to 300,000, which is commercially available from Aldrich, CAS: 25087-06-3.
  • isobutylene-maleic anhydride copolymer can be prepared according to the following literature method: Deng Cuiping, Yan Yincheng, Research on copolymerization of isobutylene-maleic anhydride, Petrochemical, 1990, 11, 739-744, the average weight of the copolymer of acrylic acid or methacrylic acid copolymerized with styrene, ethylene, vinyl alcohol, vinyl acetate, methacrylamide, isobutylene, acrylate, methacrylate or acrylonitrile The molecular weight is 500-100,000, which can be purchased directly from commercial sources, or prepared according to the methods in the following literature or books: Chen Jun, Ren Tianrui, Yu Songrui, etc., Acrylic Copolymer Synthesis and dispersion of powders, Journal of Process Engineering, 2009, 6, 1204-1209; Yanrui Xuan, water-soluble polymer,
  • Example 1 Using Method 1 to prepare a silica with a amide group on one side and a phenyl group on the other side Janus sheet material
  • the machine was emulsified by shearing at 100 rpm for 10 min, and the obtained emulsion was transferred to a three-necked flask in a water bath at 70 ° C, and mechanically stirred for 12 hours to discharge, directly obtaining an amine group on one side and a phenyl side on the other side.
  • Different Janus structure sheet materials An electron micrograph of the material is shown in Figure 1.
  • the material has a thickness of 200-400 nm and a length and a width of 2-10 ⁇ m ; the weight ratio of the material on the front surface of the substrate to the aminopropyl group and the material on the opposite surface of the substrate (which is a phenyl group) is 2: 1;
  • the material has a porous structure with a pore diameter of 5-7 nm.
  • the Janus structure sheet material having the amine side on one side and the other side of the phenyl group on the other side can be used to emulsify paraffin wax (melting point 52-54 ° C) / water system to prepare the preparation.
  • Paraffin The continuous phase, the water is the emulsion of the continuous phase, the specific method is as follows: 20 g of paraffin is heated to 70 ° C to melt, 0.5 g of the Janus piece with an amine group on one side and a phenyl group on the other side The material was added to 50 mL of water at 70 ° C and dispersed uniformly.
  • FIG. 21 is a polarizing microscope photograph of the emulsion, and the Janus sheet is seen from the figure. The material acts as an emulsifier.
  • a sheet of Janus structure having an amine group on one side and a different side on the other side of the phenyl group can be used to induce the preparation of polymethyl methacrylate (PMMA) / polystyrene (PS).
  • PMMA polymethyl methacrylate
  • PS polystyrene
  • the layered material is as follows: 180 g of polymethyl methacrylate (weight average molecular weight of 80,000 to 150,000), 180 g of polystyrene (weight average molecular weight of 100,000 to 200,000), and 40 g of the obtained sheet prepared in this example
  • the material was added to a twin-screw mixer, and kneaded at 50 ° C for 10 min at 210 ° C, and then extruded to obtain a silica sheet-like material modified polymethyl methacrylate / polystyrene.
  • Layered material is a polymethyl methacrylate / silica / polystyrene / silica alternating layer structure. An electron micrograph of the material is shown in Figure 20.
  • the Janus structure sheet material with the amine side on one side and the other side of the phenyl group on the other side can be used for the separation of oil and water by the method.
  • the specific method is as follows: Take 0.2g of the preparation sheet prepared in this example. The material was emulsified into 10 ml of toluene and 5 mL of water to form a stable emulsion. The aqueous phase was dyed orange with methyl orange to distinguish the oil-water two phases. The continuous phase water was able to flow out through the glass sand, and the toluene was prepared in this example.
  • the droplet formed under the action of the stabilization due to its large size, cannot flow through the pores at the bottom of the glass sand, still in the separation column, and then the glass jar is used to smash the Janus sheet stable oil droplets in the separation column, and the toluene can pass through the glass.
  • the bottom of the sand flows out, and the Janus piece remains in the separation column, thereby achieving separation of the oil-water two phases of the emulsion and recovery of the Janus piece.
  • the results obtained are shown in Figure 22.
  • the oil-water two-phase separation of the Janus stable emulsion makes the Janus tablet more advantageous than molecular emulsifiers in tertiary oil recovery, wastewater treatment, and splash cleaning.
  • the material has a thickness of 100-300 and a width of l- ⁇ ; the weight ratio of the material (which is an epoxy group) on the front surface of the substrate to the material (which is a phenyl group) on the reverse surface of the substrate is 1 : 1
  • the material has a thickness of 50-100 nm, a length and a width of 200 ⁇ - 5 ⁇ ; a material on the front surface of the substrate (which is an amine propyl group) and a weight of a material (which is a phenyl group) on the reverse surface of the substrate.
  • the ratio is 1:1.
  • the sodium salt hydrolyzate aqueous solution of the styrene-maleic anhydride copolymer used in this example was prepared as follows: 100 mL of toluene was added to a three-necked flask, oxygen was removed by nitrogen for 30 min, and 10 g of styrene and 10 g of maleic anhydride were added. The mixture was stirred and dissolved at room temperature, and O. lg azobisisobutyronitrile was added as an initiator, and the reaction was carried out at 90 ° C for 3 h.
  • the product was washed with suction at room temperature, and the obtained white powder was vacuum dried at 60 ° C to obtain a styrene-maleic anhydride copolymer; 10 g of the styrene-maleic anhydride copolymer was placed in a single-mouth bottle, and 5 g of hydrogen was added.
  • HSMA aqueous solution styrene-maleic anhydride copolymer
  • Example 4 Using Method 1 to prepare a porous silica with an amine group on one side and a phenyl group on the other side Janus sheet material
  • the material has a thickness of 200-500 nm, a length and a width of l- ⁇ ; a material on the front surface of the substrate (which is an amine propyl group) and a weight of a material (which is a phenyl group) on the reverse surface of the substrate.
  • the ratio is 1:1.
  • the Janus structure sheet material with different side properties has a sheet thickness of 200 nm.
  • the above-mentioned sheet material was repeatedly washed with water and ethanol, and the surfactant was washed away to obtain a porous Janus structure sheet material.
  • An electron micrograph of the material is shown in Figure 6.
  • the material has a thickness of 50-80 nm, a length and a width of 300 ⁇ - 5 ⁇ ; a material on the front surface of the substrate (which is an amine propyl group) and a material on the reverse surface of the substrate (which is an octadecyl group).
  • the weight ratio is 2:1; the material has a porous structure with a pore diameter of 5-7 nm.
  • Example 6 An organic Janus structure sheet material having a polyoxypropylene segment on one side and a polyethylene glycol segment on the other side was prepared by the second method.
  • polyethylene glycol-polybutadiene-polyoxypropylene triblock copolymer weight average molecular weight 500-20000, polyoxypropylene is a hydrophobic segment, polyethylene glycol is a hydrophilic segment, polybutan
  • the olefin is a reactive segment) dispersed in 100 mL of deionized water to obtain an aqueous solution of a glycol-butadiene-polyoxypropylene triblock copolymer, and 20 mL of decane is added to the above aqueous solution, followed by emulsification for 10 min to obtain The emulsion was stabilized, and the emulsion was irradiated with ultraviolet light for 30 minutes to obtain hollow microspheres of Janus structure.
  • the emulsion was freeze-dried and then ground into a sheet at a low temperature to obtain a polyoxypropylene segment on one side and a polyethylene glycol chain on the other side. Segment of the organic Janus structure sheet material.
  • An electron micrograph of the material is shown in Figure 7.
  • the material has a thickness of 30-200 nm and a length and a width of 200 ⁇ - 5 ⁇ ; the weight ratio of the material (which is polyethylene glycol) on the front surface of the substrate to the material (polyoxypropylene) on the reverse surface of the substrate is 1 : 1.
  • Example 7 An organic Janus structure sheet material having a polystyrene chain on one side and a polymethyl methacrylate chain on the other side was prepared by the second method.
  • styrene-butadiene-methyl methacrylate amphiphilic triblock graft polymer weight average molecular weight 2000-0000, CAS: 25053-09-2, purchased from Sigma, where hydrophilic polymer
  • the segment is polymethyl methacrylate, the reactive olefin or alkyne polymer segment is polybutadiene, the hydrophobic polymer segment is the polystyrene segment in the block copolymer
  • 50mL In the non-polar solvent n-hexane, 10 mL of a 0.01% by weight aqueous solution of potassium persulfate was added to the above solution, and emulsified by ultrasonication for 10 min to obtain a stable emulsion, and the temperature was raised to 70 ° C.
  • the Janus structure was hollow. Microspheres.
  • the emulsion was freeze-dried and then ground at a low temperature to obtain a Janus structure sheet material having a polystyrene chain on one side and a polymethyl methacrylate chain on the other side.
  • the material has a thickness of 20-50 nm, a length and a width of 100 ⁇ - 2 ⁇ ; a weight of the material on the front surface of the substrate (polystyrene) and a material on the opposite surface of the substrate (polymethyl methacrylate). The ratio is 1:1.
  • Example 8 Preparation of urea-formaldehyde resin by method three / polystyrene Janus sheet material
  • O. lg initiator used in the reaction of the reaction system was carried out at 30 ° C for 12 h under the protection of nitrogen.
  • the potassium persulfate and the O. lg initiator sodium bisulphite initiate a free radical polymerization reaction to obtain a styrene polymer, and then raise the reaction temperature to 70 ° C to cause the urea-formaldehyde prepolymer to undergo a polycondensation reaction, and continue the reaction for 8 hours.
  • the emulsion was cooled by ice water, suction filtered, and vacuum dried to obtain a urea-formaldehyde resin/polystyrene composite polymer hollow microsphere.
  • the hollow microspheres were ground to a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the urea-formaldehyde resin/polystyrene composite.
  • An electron micrograph of the material is shown in Figure 8.
  • the material has a thickness of 30-60 nm, a length and a width of 500 ⁇ - 5 ⁇ ; a weight ratio of a material (which is polystyrene) on the front surface of the substrate to a material (a urethane resin) on the reverse surface of the substrate is 3 : 2.
  • the urea-formaldehyde prepolymer aqueous solution is prepared according to the following method: 240 g of urea and 500 g of a 37% by mass aqueous formaldehyde solution are added to a three-necked flask equipped with a reflux condenser, and mechanically dissolved and dissolved. Adding triethanolamine to adjust the pH of the system to 8, heating to 70 ° C, holding the reaction for 1 h to obtain a viscous liquid, and adding 1000 g of water to dilute to obtain a stable urea-formaldehyde prepolymer aqueous solution.
  • Example 9 Preparation of melamine resin by using Method 3 / Polybutadiene Janus sheet material
  • step 2) Under the protection of nitrogen, the reaction system of step 1) is reacted at 30 ° C for 12 h, using O. lg initiator potassium persulfate and O. lg initiator sodium hydrogen sulfite to initiate free radical polymerization to obtain polybutadiene.
  • Polymer then raise the reaction temperature to 70 ° C, the melamine-formaldehyde prepolymer is polycondensed, continue the reaction for 8h, the emulsion is cooled by ice water, suction filtration, vacuum drying, to obtain melamine resin / polybutadiene Composite polymer hollow microspheres.
  • the hollow microspheres are ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the melamine resin/polybutadiene composite.
  • the material has a thickness of 20-100 nm and a length and a width of 100 ⁇ - 2 ⁇ ; the weight ratio of the material on the front surface of the substrate (which is a melamine resin) to the material on the reverse surface of the substrate (which is polybutadiene) is 3: 2.
  • the melamine-formaldehyde prepolymer aqueous solution is prepared according to the following method: 110 g of melamine and 500 g of 37% aqueous formaldehyde solution are added to a three-necked flask equipped with a reflux condenser, mechanically stirred to dissolve, and triethanolamine is added to adjust the pH of the system. 8, heated to 70 ° C, the reaction was incubated for 1 h to obtain a viscous liquid, and then diluted with 1000 g of water to obtain a stable aqueous solution of melamine-formaldehyde prepolymer.
  • the urea-formaldehyde prepolymer aqueous solution used was prepared in accordance with the method of Example 6.
  • the material has a thickness of 20-60 nm and a length and a width of 100-800 nm; the weight ratio of the material (which is polystyrene) on the front surface of the substrate to the material (for the urethane resin) on the reverse surface of the substrate is 1 : 1.
  • the material has a thickness of 100-500 nm, a length and a width of 300 ⁇ - 5 ⁇ ; a material on the front surface of the substrate (which is silica) and a material on the reverse surface of the substrate (the weight ratio of the melamine resin is 1: 10.
  • Example 12 Preparation of Titanium Dioxide / Urea Resin by Method 4 Janus Sheet Material
  • the material has a thickness of 50-200 nm and a length and a width of 400 ⁇ - 10 ⁇ ; the weight ratio of the material (which is titanium dioxide) on the front surface of the substrate to the material (for the urethane resin) on the reverse surface of the substrate is 1:3. .
  • Aqueous formaldehyde prepolymer aqueous solution was prepared according to the method provided in Example 6.
  • the material has a thickness of 60-380 nm, a length and a width of 500 ⁇ - 10 ⁇ ; a weight ratio of a material (as silica) on the front surface of the substrate to a material (for urea-formaldehyde resin) on the reverse surface of the substrate is 2: 5.
  • the material has a thickness of 100-400 nm and a length and a width of l- ⁇ ; the weight ratio of the material (which is silicon dioxide) on the front surface of the substrate to the material (polystyrene) on the reverse surface of the substrate is 2 : 5.
  • the material has a thickness of 40-200 nm, a length and a width of 300 ⁇ - 8 ⁇ ; a weight ratio of a material (which is silicon dioxide) on the front surface of the substrate to a material (polydivinylbenzene) on the reverse surface of the substrate. It is 1:1.
  • Disperse the solvent solvent n-hexane use a high-speed shear emulsifier to shear emulsified lOmin at 12000r/min, transfer the obtained emulsion to a three-necked bottle in a 50°C water bath, and mix it with mechanical agitation, then take 20g of mass concentration to 5 % of the aqueous solution of the resin prepolymer urea-formaldehyde prepolymer dissolved in the continuous phase solvent water, dissolved in 2 g of sodium chloride, adjusted to pH 6 with 1 M hydrochloric acid, slowly dropped into the above emulsion, lOmin was added dropwise After completion, 50 ° C constant temperature polycondensation reaction for 1 h, slowly adjust the pH of the system to 3.5 with 1M hydrochloric acid, continue the polycondensation reaction for 4 h, in dispersion a water-insoluble polycondensate of a crosslinked three-dimensional network structure is formed at the interface between the phase
  • the hollow microspheres obtained in the step 2) are ground into pieces at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the urea/melamine composite.
  • An electron micrograph of the material is shown in Figure 12.
  • the material has a thickness of 30-100 nm, a length and a width of 200 ⁇ - 10 ⁇ ; a weight ratio of a material on the front surface of the substrate (for urea-formaldehyde resin) to a material on the opposite surface of the substrate (melamine resin) is 1: 1.
  • the sodium salt hydrolyzate aqueous solution of the styrene-maleic anhydride copolymer used is prepared according to the method provided in Example 4, and the melamine-formaldehyde prepolymer aqueous solution is prepared according to the method provided in Example 5.
  • a urea-formaldehyde prepolymer aqueous solution was prepared according to the method provided in Example 6.
  • the polycondensate obtained in step 1) and the gelatin molecule are electrostatically attracted, and a new shell layer is formed on the outer side of the primary shell layer obtained in the step 1).
  • the capsule shell layer is initially cross-linked and solidified, and then the emulsion is suction filtered and vacuum dried to obtain a polyethylene glycol-modified urine aldehyde resin/gelatin composite polymer hollow microsphere.
  • the hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the polyethylene glycol modified urethane tree/gelatin composite. An electron micrograph of the material is shown in Figure 13.
  • the material has a thickness of 50 nm to 200 nm, a length and a width of 200 ⁇ - 5 ⁇ ; a material on the front surface of the substrate (polyethylene glycol modified urethane resin) and a material on the reverse surface of the substrate (gelatin)
  • the weight ratio is 3:1.
  • the polyethylene glycol modified urea-formaldehyde prepolymer aqueous solution used is prepared as follows: 240 g of urea, 50 g of polyethylene glycol and 450 g of 37% aqueous formaldehyde solution are added to a three-necked flask equipped with a reflux condenser. , mechanical stirring and dissolution, adding triethanolamine to adjust the pH value of 8, to 70 ° C, the reaction reaction for 1 h to obtain a viscous liquid, and then adding 1000 g of water to dilute, to obtain a stable polyethylene glycol modified urea-formaldehyde prepolymerization Aqueous solution.
  • the weight ratio of the material (which is a urethane resin) on the front surface of the substrate to the material (which is a urea-formaldehyde resin) on the reverse surface of the substrate is 3:2.
  • a 37% aqueous solution of formaldehyde was reacted for 3 hours to crosslink and cure the capsule shell.
  • the emulsion was cooled by ice water, filtered, and vacuum dried to obtain an epoxy resin/polyvinylpyrrolidone composite polymer hollow microsphere.
  • the hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the epoxy resin/polyvinylpyrrolidone composite.
  • An electron micrograph of the material is shown in Figure 15. Among them, an aqueous solution of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer was prepared in accordance with the method provided in Example 3.
  • the material has a thickness of 30-200 nm, a length and a width of 300 ⁇ - 10 ⁇ ; a weight ratio of a material (which is an epoxy resin) on the front surface of the substrate to a material (for polyvinylpyrrolidone) on the reverse surface of the substrate is 40 : 1.
  • the emulsion was transferred and emulsified for 10 min, and the emulsion was transferred to a three-necked flask equipped with a reflux condenser in a constant temperature water bath at 70 ° C, and mechanically uniformly stirred. To the emulsion was added dropwise O.
  • initiator potassium persulfate (dispersed phase radical polymerization)
  • a 20g aqueous solution having a mass ratio of monomeric styrene to divinylbenzene and an initiator of 150:1) reacted at 70 ° C for 8 hours under the protection of nitrogen, the initiator initiates free radical polymerization of the dispersed phase
  • the monomer undergoes radical polymerization to form a polymer, and the polymer is phase-separated and deposited at the interface between the dispersed phase and the continuous phase to form a crosslinked three-dimensional network polymer shell, that is, a primary shell layer;
  • the hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the polystyrene/urea resin composite.
  • a urea-formaldehyde prepolymer aqueous solution was prepared in accordance with the method provided in Example 6.
  • An electron micrograph of the material is shown in Figure 16.
  • the material has a thickness of 50-300 nm, a length and a width of 500 ⁇ - 15 ⁇ ; a weight ratio of a material (which is polystyrene) on the front surface of the substrate to a material (which is a urea-formaldehyde resin) on the reverse surface of the substrate is 3: 2.
  • the initiator initiates radical polymerization of the free-radical polymerization monomer of the dispersed phase to form a polymer, which produces a phase Separating and depositing at the interface between the dispersed phase and the continuous phase to form a crosslinked three-dimensional network polymer shell layer, that is, a primary shell layer;
  • the new shell layer continue to coagulate reaction lh; the system is placed in an ice water bath, and then added 2mL 37% aqueous formaldehyde solution for 3h, the capsule shell layer cross-linking solidified, the emulsion is cooled by ice water, suction filtration, vacuum drying , obtaining polydivinylbenzene/gelatin composite polymer hollow microspheres.
  • the hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the polydivinylbenzene/gelatin composite. An electron micrograph of the material is shown in Figure 17.
  • the material has a thickness of 30-100 nm, a length and a width of 500 ⁇ - 5 ⁇ ; a weight ratio of a material (for polydivinylbenzene ) on the front surface of the substrate to a material (for gelatin) on the reverse surface of the substrate is 5 : 1.
  • Example 22 Preparation of gelatin / sodium alginate using Method 5 Janus sheet material
  • the system was placed in an ice water bath, then 1 mL of 37% aqueous formaldehyde solution was added and reacted for 3 hours to preliminarily crosslink and cure the capsule shell.
  • the emulsion was cooled with ice water, suction filtered, and vacuum dried to obtain a gelatin/alginate nanocomposite hollow microsphere.
  • the hollow microspheres were ground into a sheet at a low temperature to obtain a Janus structure sheet material having different compositions on both sides of the gelatin/alginate nano composite. An electron micrograph of the material is shown in Figure 18.
  • the material has a thickness of 30-150 nm, a length and a width of 500 ⁇ - 5 ⁇ ; a weight ratio of a material (as gelatin) on the front surface of the substrate to a material (in the form of sodium alginate) on the opposite surface of the substrate is 1:1. .
  • an aqueous solution of a sodium salt hydrolyzate of a styrene-maleic anhydride copolymer used was prepared in accordance with the method provided in Example 3.
  • step 2) The emulsion obtained in step 1) is reacted under mechanical stirring in a 40 ° C water bath for 12 h, and then the emulsion is cooled by ice water, suction filtered, vacuum dried, and the polyacrylamide/polystyrene composite is directly obtained.
  • Example 24 Preparation of Crosslinked Polyacrylamide/Crosslinked Polystyrene Janus Sheet Material by Method 6 1) Take 5 g of free radical polymerizable monomer acrylamide dissolved in polar solvent water, 0.5 g dissolved in polar solvent water Free radical polymerization initiator ferrous sulfate, O.
  • lg free radical polymerizable monomer in polar solvent water ⁇ , ⁇ -dimethyl bis acrylamide, lg emulsifier cetyl trimethyl bromide ( CTAB) was added to 200g of polar solvent water and mixed well as an aqueous phase; 2g of free radical polymerizable monomer divinylbenzene dissolved in non-polar solvent decane, 2g dissolved in non-polar solvent decane Free radical polymerization monomer styrene, 2g soluble in non-polar
  • the free radical polymerization initiator in solvent decane is dissolved in 50 g of non-polar solvent decane as an oil phase; the aqueous phase is added to the oil phase, and the emulsion is sheared at 12000 rpm using a high-speed shear emulsifier.
  • step 2) The emulsion obtained in step 1) is reacted under mechanical stirring in a 40 ° C water bath for 6 h, and the emulsion is cooled with ice water, suction filtered, and vacuum dried to obtain crosslinked polyacrylamide/crosslinking.
  • the front and back sides of the polystyrene composite have different compositions of Janus structure sheet materials.
  • the material has a thickness of 50-200 nm, a length and a width of 500 ⁇ - 10 ⁇ ; a material on the front surface of the substrate (which is a cross-linked polyacrylamide) and a material on the opposite surface of the substrate (which is a cross-linked polystyrene)
  • the weight ratio is 5:2.
  • Example 25 Preparation of Polymethyl Methacrylate / Polyvinyl Alcohol by Method Six Janus Sheet Material
  • the material has a thickness of 50-300 nm, a length and a width of 500 ⁇ - 10 ⁇ ; a weight of the material on the front surface of the substrate (polymethyl methacrylate) and a material on the opposite surface of the substrate (polyvinyl alcohol). The ratio is 2: 1.
  • the invention prepares the spherical shell by materializing the emulsion oil-water interface, that is, forming inorganic materials, organic materials and inorganic and organic composite hollow microspheres by chemical reaction or physical adsorption at the interface between the discontinuous phase and the continuous phase of the emulsion.
  • Hollow microspheres having different inner and outer surface structures or compositions; the shell layer may be continuous or discontinuous.
  • the shell layer may be continuous or discontinuous.
  • the size of the fragments can be achieved by controlling the grinding process.
  • the thickness of the fragments can be achieved by controlling the concentration of the reactants.
  • the shell can be used directly as a shell.
  • the above-mentioned sheet material is used, and it can be further used for grinding.
  • the thickness and size of the sheet are related to conditions such as the concentration of the reactant.
  • a sheet material can also be prepared as a Janus structure sheet material having a cell structure, and both sides of the sheet material have different cell structures due to differences in structure and composition.
  • the method is a universal preparation method for preparing a sheet material having different properties on the front and back surfaces on a large scale.
  • the Janus sheet material provided by the invention has important application value in many fields due to its different composition and properties on both sides.
  • Janus sheet replaces ordinary polymer inorganic filler and polymer blending compatibilizer
  • Janus sheet material can simultaneously combine inorganic filler and polymer blending compatibilizer, which is beneficial to the formation of layered polymer, and It plays a role in increasing polymer compatibility and enhancing toughening.
  • Janus sheet material can also be used to prepare emulsions instead of traditional surfactants as emulsifiers, and because Janus sheet materials are different from molecular surfactants, Janus sheet materials can be used as emulsifiers. Special types of emulsions such as ultra-concentrated emulsions are obtained, which are of great significance in practical application and theoretical research.

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Abstract

L'invention porte sur des matériaux sous forme d'écaille ayant des propriétés différentes sur leurs côtés avant et arrière (ce qu'on appelle également une structure biface) et sur leur procédé de préparation. Dans le procédé de préparation, une sphère creuse de matériau non organique, organique et composite non organique/organique est formée par matérialisation de l'interface huile-eau d'une émulsion, à savoir au moyen d'une réaction chimique ou d'une absorption physique survenant à l'interface entre une phase dispersée et la phase continue de l'émulsion, afin de préparer des structures de surface interne et externe d'une enveloppe ou construction sphérique différente de microsphères creuses. Lesdites écailles à structure biface peuvent être ensuite obtenues par fragmentation. L'invention porte également sur un procédé largement adaptable pour la préparation massive des écailles à structure biface. Le matériau sous forme d'écaille de cette invention présente une grande valeur pratique dans de nombreux domaines du fait de ses composition et propriétés différentes sur les côtés avant et arrière.
PCT/CN2011/000081 2010-01-21 2011-01-19 Matériau sous forme d'écaille ayant des propriétés différentes sur ses côtés avant et arrière et son procédé de préparation Ceased WO2011088743A1 (fr)

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CN110756132A (zh) * 2019-10-31 2020-02-07 大连理工大学 一种核壳磁性微球的制备方法
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GB2609582A (en) * 2021-09-24 2023-02-08 Univ Jiangsu Preparation method of circular nanosheet with high-density sites, and use of circular nanosheet in adsorption of blood lead
GB2609582B (en) * 2021-09-24 2024-04-24 Univ Jiangsu Preparation method of circular nanosheet with high-density sites, and use of circular nanosheet in adsorption of blood lead

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